Mass polymerizable polycycloolefin compositions containing soluble photoacid generators

ABSTRACT

Embodiments in accordance with the present invention encompass compositions comprising a soluble photoacid generator, a organopalladium compound, a photosensitizer and one or more olefinic monomers which undergo vinyl addition polymerization when said composition is exposed to a suitable actinic radiation to form a substantially transparent film. The monomers employed therein have a range of optical and mechanical properties, and thus these compositions can be tailored to form films having various opto-electronic properties. Accordingly, compositions of this invention are useful in various applications, including as coatings, encapsulants, fillers, leveling agents, among others.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.63/036,078, filed Jun. 8, 2020, which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION Field of the Invention

Embodiments in accordance with the present invention relate generally tomass polymerizable polycycloolefin monomer compositions containingsoluble photoacid generators having utility in such applications asoptical sensors, light emitting diodes (LEDs), organic light emittingdiode (OLED), among others. More specifically, this invention relates tosingle component compositions encompassing primarily non-polarnorbornene (NB) based olefinic monomers, which undergo mass vinyladdition or ring open metathesis polymerization in the presence ofsoluble photoacid generators and palladium or ruthenium catalysts whichwhen photolyzed forms optical layers having utility in a variety ofopto-electronic applications including as encapsulants, coatings, andfillers.

Description of the Art

Organic light emitting diodes (OLEDs) are gaining importance in avariety of applications, including flat panel televisions and otherflexible displays, among other applications. However, conventionalOLEDs, particularly, bottom emitting OLEDs suffer from a drawback inthat only about half of the generated photons are emitted into the glasssubstrate out of which 25% are extracted into air. The other half of thephotons are wave-guided and dissipated in the OLED stack. This loss ofphotons is primarily attributed to the refractive index (n) mismatchbetween the organic layers (n=1.7-1.9) and the glass substrate (n=1.5).By matching the refractive index of the substrate (n=1.8) and organiclayers and augmenting the distance of the emission zone to the cathodeto suppress plasmonic losses light extraction into the substrate can beincreased to 80-90%. See, for example, G. Gaertner et al., Proc. OfSPIE, Vol. 6999, 69992T pp 1-12 (2008).

In addition, OLEDs also pose other challenges; in that OLEDs beingorganic materials, they are generally sensitive to moisture, oxygen,temperature, and other harsh conditions. Thus, it is imperative thatOLEDs are protected from such harsh atmospheric conditions. See forexample, U. S. Patent Application Publication No. US2012/0009393 A1.

In order to address some of the issues faced by the art, U.S. Pat. No.8,263,235 discloses use of a light emitting layer formed from at leastone organic light emitting material and an aliphatic compound not havingan aromatic ring, and a refractive index of the light emitting from 1.4to 1.6. The aliphatic compounds described therein are generally avariety of polyalkyl ethers, and the like, which are known to beunstable at high temperatures, see for example, Rodriguez et al., I & ECProduct Research and Development, Vol. 1, No. 3, 206-210 (1962).

U.S. Pat. Nos. 9,944,818 and 10,266,720, disclose a two component masspolymerizable composition which is capable of tailoring to the desirablerefractive index and is suitable as a filler and a protective coatingmaterial, thus potentially useful in the fabrication of a variety ofOLED devices.

U.S. Pat. No. 10,626,198 B2, discloses a single component mass vinyladdition polymerizable composition which is thermally activated andcapable of tailoring to the desirable refractive index and is suitableas a filler and a protective coating material, thus potentially usefulin the fabrication of a variety of OLED devices.

However, there is still a need for organic filler materials thatcomplement the refractive index of OLEDs and yet exhibit hightransparency and good thermal properties, among other desirableproperties. In addition, it is desirable that such organic fillermaterials readily form a permanent protective coatings and are availableas a single component composition for dispensing with such OLED layerssimply by exposing to suitable actinic radiation at ambient temperature.

It has been observed in some of these compositions the photoacidgenerator which is generally employed to mass polymerize the cyclicolefinic monomer is not soluble in such compositions thus rendering thecompositions unsuitable for a variety of applications.

Thus, it is an object of this invention to provide organic materialsthat overcome the gaps faced by the art. More specifically, it is anobject of this invention to provide a single component composition thatwill mass polymerize when exposed to suitable actinic radiation underthe conditions of the fabrications of an OLED device. It is further anobject of this invention to provide stable single component masspolymerizable composition with no change in viscosity at or below normalstorage conditions but which undergoes mass polymerization only whenexposed to suitable actinic radiation, and where the photoacid generatorutilized is completely miscible in the composition.

It is further an object of this invention to provide single componentcomposition that can be used in a variety of other applicationsincluding for example 3D printing, ink-jettable coatings, sealants, andthe like.

Other objects and further scope of the applicability of the presentinvention will become apparent from the detailed description thatfollows.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that by employing a single componentcomposition, where a photoacid generator is completely miscible in thecomposition and thereby it is now possible to fabricate a variety ofdevices including for example an OLED device having a transparentoptical layer which features hitherto unachievable properties, i.e.,refractive index in the range of 1.4 to 1.6 or higher, high colorlessoptical transparency, desirable film thickness of the filler layertypically in the range of 10 to 20 μm but can be tailored to lower orhigher film thickness depending upon the intended application,compatible with the OLED stack, particularly the cathode layer (a verythin layer on the top of the OLED stack), compatible with polymerizationof the formulation on the OLED stack, including fast polymerization timeand can be photolytically treated at ambient fabrication conditions,adhesion to both OLED stack and glass cover, and the like. It is alsoimportant to note that the compositions of this invention are expectedto exhibit good uniform leveling across the OLED layer which typicallyrequires a low viscosity. Further, compositions of this invention arealso expected to exhibit low shrinkage due to their rigidpolycycloolefinic structure. In addition, as the components of thisinvention undergo fast mass polymerization upon application they do notleave behind any fugitive small molecules which can damage the OLEDstack. Generally, no other small molecule additives need to be employedthus offering additional advantages. Most importantly, the compositionsof this invention are stable (i.e., no change in viscosity) at ambientatmospheric conditions including up to 40° C. for several days to weeksand undergo mass polymerization only when exposed to suitable actinicradiation. The compositions undergo mass vinyl addition polymerizationvery quickly when subjected to such actinic radiation and generally thecompositions become solid objects in few minutes, i.e., within 1-10minutes and more generally in less than one hour.

Advantageously, the compositions of this invention are also compatiblewith a “one drop fill” (commonly known as “ODF”). In a typical ODFprocess, which is commonly used to fabricate a top emission OLED device,a special optical fluid is applied to enhance the transmission of lightfrom the device to the top cover glass, and the fluid is dispensed by anODF method. Although the method is known as ODF which can be misleadingbecause several drops or lines of material are generally dispensedinside the seal lines. After applying the fluid, the fluid spreads outas the top glass is laminated, analogous to die-attach epoxy. Thisprocess is generally carried out under vacuum to prevent air entrapment.The present invention allows for a material of low viscosity whichreadily and uniformly coats the substrate with rapid flow in a shortperiod of time. Even more advantageously, the present inventionovercomes the deficiencies faced by the prior art in that a singlecomponent composition is much more convenient than employing a twocomponent system especially in an ODF method.

Accordingly, there is provided a single component compositionencompassing a) a soluble photoacid generator of formula (I) or (II); b)an organopalladium compound of formula (III), an organopalladiumcompound of formula (IIIA) or an organopalladium compound of formula(IIIB) as described herein; c) one or more olefinic monomers of formula(V); and d) a photosensitizer.

In another aspect of this invention there is also provided a kitencompassing the composition of this invention for forming a threedimensional object, such as for example, a transparent film.

DETAILED DESCRIPTION

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, the symbol “

” denotes a position at which the bonding takes place with anotherrepeat unit or another atom or molecule or group or moiety asappropriate with the structure of the group as shown.

As used herein, “hydrocarbyl” refers to a group that contains carbon andhydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl,aralkyl, alkaryl, and alkenyl. The term “halohydrocarbyl” refers to ahydrocarbyl group where at least one hydrogen has been replaced by ahalogen. The term perhalocarbyl refers to a hydrocarbyl group where allhydrogens have been replaced by a halogen.

As used herein, the expression “(C₁-C₆)alkyl” includes methyl and ethylgroups, and straight-chained or branched propyl, butyl, pentyl and hexylgroups. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyland tert-butyl. Derived expressions such as “(C₁-C₄)alkoxy”,“(C₁-C₄)thioalkyl” “(C₁-C₄)alkoxy(C₁-C₄)alkyl”, “hydroxy(C₁-C₄)alkyl”,“(C₁-C₄)alkylcarbonyl”, “(C₁-C₄)alkoxycarbonyl(C₁-C₄)alkyl”,“(C₁-C₄)alkoxycarbonyl”, “diphenyl(C₁-C₄)alkyl”, “phenyl(C₁-C₄)alkyl”,“phenylcarboxy(C₁-C₄)alkyl” and “phenoxy(C₁-C₄)alkyl” are to beconstrued accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic groups. Representative examples of “cycloalkyl” includes withoutany limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “(C₁-C₆)perfluoroalkyl” means that all ofthe hydrogen atoms in said alkyl group are replaced with fluorine atoms.Illustrative examples include trifluoromethyl and pentafluoroethyl, andstraight-chained or branched heptafluoropropyl, nonafluorobutyl,undecafluoropentyl and tridecafluorohexyl groups. Derived expression,“(C₁-C₆)perfluoroalkoxy”, is to be construed accordingly. It shouldfurther be noted that certain of the alkyl groups as described herein,such as for example, “(C₁-C₆)alkyl” may partially be fluorinated, thatis, only portions of the hydrogen atoms in said alkyl group are replacedwith fluorine atoms and shall be construed accordingly.

As used herein, the expression “(C₆-C₁₀)aryl” means substituted or=substituted phenyl or naphthyl. Specific examples of substituted phenylor naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl,1-methylnaphthyl, 2-methylnaphthyl, etc. “Substituted phenyl” or“substituted naphthyl” also include any of the possible substituents asfurther defined herein or one known in the art.

As used herein, the expression “(C₆-C₁₀)aryl(C₁-C₄)alkyl” means that the(C₆-C₁₀)aryl as defined herein is further attached to (C₁-C₄)alkyl asdefined herein. Representative examples include benzyl, phenylethyl,2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of (C₁-C₆)alkyl, (C₂-C₆)alkenyl,(C₁-C₆)perfluoroalkyl, phenyl, hydroxy, —CO₂H, an ester, an amide,(C₁-C₆)alkoxy, (C₁-C₆)thioalkyl and (C₁-C₆)perfluoroalkoxy. However, anyof the other suitable substituents known to one skilled in the art canalso be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

By the term “derived” is meant that the polymeric repeating units arepolymerized (formed) from, for example, polycyclic norbornene-typemonomers in accordance with formulae (I) to (IV) wherein the resultingpolymers are formed by 2,3 enchainment of norbornene-type monomers asshown below:

Accordingly, in accordance with the practice of this invention there isprovided a single component composition encompassing

a) a soluble photoacid generator selected from the group consisting of

a compound of formula (I):

and

a compound of formula (II):

wherein:

a is an integer from 1 to 5;

An^(⊖) is selected from the group consisting of Cl^(⊖), Br^(⊖), I^(⊖),BF₄ ^(⊖), tetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,(triphenylsiloxy)tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate,tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]pheny-l]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate,tris(trifluoromethanesulfonyl)methide,bis(trifluoromethanesulfonyl)imide, PF₆ ^(⊖), SbF₆ ^(⊖), n-C₄F₉SO₃ ^(⊖),CF₃SO₃ ^(⊖) and p-CH₃(C₆H₄)—SO₃ ^(⊖);

at least one of R₈, R₉, R₁₀, R₁₁ and R₁₂ is selected from the groupconsisting of linear or branched (C₁₀-C₂₀)alkyl,(C₆-C₁₀)aryl(C₁₀-C₂₀)alkyl, (C₁₀-C₂₀)alkoxy,(C₆-C₁₀)aryloxy(C₁₀-C₂₀)alkyl, (C₁₀-C₂₀)alkanoyl(C₆-C₁₀)aryl and(C₁₀-C₂₀)alkoxy(C₆-C₁₀)aroyl(C₆-C₂₀)alkyl; and

the remaining R₈, R₉, R₁₀, R₁₁ and R₁₂ are the same or different andeach independently selected from the group consisting of halogen,methyl, ethyl, linear or branched (C₃-C₂₀)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₆-C₁₀)-aryloxy, (C₆-C₁₀)thioaryl,(C₁-C₆)alkanoyl(C₆-C₁₀)thioaryl, (C₁-C₆)alkoxy(C₆-C₁₀)aroyl(C₁-C₆)alkyland (C₆-C₁₀)thioaryl-(C₆-C₁₀)diarylsulfonium salt;

b) an organopalladium compound selected from the group consisting of acompound of formula (III), a compound of formula (IIIA) and a compoundof formula (IIIB):

wherein:

L is a ligand selected from the group consisting of P(R)₃, P(OR)₃,O═P(R)₃, RCN and substituted or unsubstituted pyridines, where R isselected from the group consisting of methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, (C₁-C₁₆)perfluoroalkyl, (C₃-C₁₀)cycloalkyl,(C₆-C₁₀)aryl(C₁-C₁₆)alkyl and substituted or unsubstituted (C₆-C₁₀)aryl;

each A independently is a bidentate monoanionic ligand of formula (IV):

wherein:

n is an integer 0, 1 or 2;

X and Y are independently of each other selected from O, N and S;

R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are the same or different and eachindependently selected from the group consisting of hydrogen, methyl,ethyl, linear or branched (C₃-C₁₆)alkyl, (C₁-C₁₆)perfluoroalkyl,(C₃-C₁₀)cycloalkyl, (C₆-C₁₀)aryl(C₁-C₁₆)alkyl and substituted orunsubstituted (C₆-C₁₀)aryl; provided when either X or Y is O or S, R₁and R₅, respectively, do not exist;

c) one or more olefinic monomers of the formula (V):

wherein:

m is an integer 0, 1 or 2;

is a single bond or a double bond;

at least one of R₁₃, R₁₄, R₁₅ and R₁₆ is selected from the groupconsisting of linear or branched (C₆-C₁₆)alkyl,(C₆-C₁₂)aryl(C₁-C₁₆)alkyl, (C₆-C₁₀)aryloxy(C₂-C₁₆)alkyl and(C₆-C₁₀)aryl(C₆-C₁₀)aryloxy(C₁-C₁₆)alkyl;

the remaining R₁₃, R₁₄, R₁₅ and R₁₆ are the same or different and eachindependently selected from the group consisting of hydrogen, halogen, ahydrocarbyl or halohydrocarbyl group selected from methyl, ethyl, linearor branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy,

a group of formula (A):—Z-Aryl  (A);

a group of formula (A1):

a group of formula (A2):

a group of formula (A3):

and

a group of formula (A4):

wherein:

Z is selected from the group consisting of:

-   -   O, CO, C(O)O, OC(O), OC(O)O, S, (CR₁₇R₁₈)_(b), O(CR₁₇R₁₈)_(b),        (CR₁₇R₁₈)_(b)O, C(O)(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)C(O),        C(O)O(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)C(O)O, OC(O)(CR₁₇R₁₈)_(b),        (CR₁₇R₁₈)_(b)OC(O), (CR₁₇R₁₈)_(b)OC(O)O,        (CR₁₇R₁₈)_(b)OC(O)O(CR₁₇R₁₈)_(b), OC(O)O(CR₁₇R₁₈)_(b),        S(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)S, (SiR₁₇R₁₈)_(b), O(SiR₁₇R₁₈)_(b),        (SiR₁₇R₁₈)_(b)O, where

R₁₇ and R₁₈ are the same or different and each independently selectedfrom hydrogen, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,substituted or unsubstituted (C₆-C₁₄)aryl, methoxy, ethoxy, linear orbranched (C₃-C₆)alkyloxy, (C₂-C₆)acyl, (C₂-C₆)acyloxy, and substitutedor unsubstituted (C₆-C₁₄)aryloxy; and

b is an integer from 0 to 12, inclusive;

Aryl is selected from the group consisting of substituted orunsubstituted phenyl, substituted or unsubstituted biphenyl andsubstituted or unsubstituted naphthyl, substituted or unsubstitutedterphenyl, substituted or unsubstituted anthracenyl substituted orunsubstituted fluorenyl, wherein said substituents are selected from thegroup consisting of halogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₀)aryloxy, (C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy andperfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy;

k is an integer from 1 to 12;

R₂₃, R₂₄ and R₂₅ are the same or different and each independentlyselected from the group consisting of hydrogen, methyl, ethyl, linear orbranched (C₃-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, methoxy, ethoxy, linearor branched (C₃-C₁₂)alkoxy, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl,perfluoro(C₆-C₁₀)aryl and perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl; or

R₂₃ and R₂₄ taken together with the intervening carbon atoms to whichthey are attached to form a substituted or unsubstituted (C₅-C₁₄)cyclic,(C₅-C₁₄)bicyclic or (C₅-C₁₄)tricyclic ring; and Arylene is substitutedor unsubstituted bivalent (C₆-C₁₄)aryl;

or

one of R₁ and R₂ taken together with one of R₃ and R₄ and the carbonatoms to which they are attached to form a substituted or unsubstituted(C₅-C₁₄)cyclic, (C₅-C₁₄)bicyclic or (C₅-C₁₄)tricyclic ring;

and

a) a photosensitizer.

More specifically, the Aryl as defined herein is substituted orunsubstituted biphenyl of formula:

c) substituted or unsubstituted naphthyl of formula:

e) substituted or unsubstituted terphenyl of formula:

g) substituted or unsubstituted anthracenyl of formula:

i) substituted or unsubstituted fluorenyl of formula:

k) where R_(x) in each occurrence is independently selected from methyl,ethyl, linear or branched (C₃-C₁₂)alkyl or (C₆-C₁₀)aryl.

It should be noted that the ligand, L of the organopalladium compoundsof formulae (IIIA) or (IIIB) can generally be a Lewis Base, which iscoordinately bonded to palladium. That is, the Lewis Base is bonded topalladium by sharing both of its lone pair of electrons. Accordingly,any of the Lewis Base known in the art can be used for this purpose.Advantageously, it has now been found that a Lewis Base, which candissociate readily under the polymerization conditions as describedfurther in detail below generally provides more suitable compounds offormula (IIIA) or (IIIB) as polymerization catalysts, i.e., initiators.Thus, in one aspect of this invention judicious selection of the LewisBase (LB) will provide a modulation of the catalytic activity of thecompounds of this invention.

Accordingly, it has now been found that suitable LBs that can beemployed include without any limitation substituted and unsubstitutednitriles, including alkyl nitrile, aryl nitrile or aralkyl nitrile;phosphine oxides, including substituted and unsubstituted trialkylphosphine oxides, triaryl phosphine oxides, triarylalkyl phosphineoxides, and various combinations of alkyl, aryl and aralkyl phosphineoxides; substituted and unsubstituted pyrazines; substituted andunsubstituted pyridines; phosphites, including substituted andunsubstituted trialkyl phosphites, triaryl phosphites, triarylalkylphosphites, and various combinations of alkyl, aryl and aralkylphosphites; phosphines, including substituted and unsubstituted trialkylphosphines, triaryl phosphines, triarylalkyl phosphines, and variouscombinations of alkyl, aryl and aralkyl phosphines. Various other LBsthat may be employed include various ethers, alcohols, ketones, aminesand anilines, arsines, stibines, and the like.

-   -   1) In some embodiments of this invention, the LB is selected        from acetonitrile, propionitrile, n-butyronitrile,        tert-butyronitrile, benzonitrile (C₆H₅CN),        2,4,6-trimethylbezonitrile, phenyl acetonitrile (C₆H₅CH₂CN),        pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine,        2,3-dimethylpyridine, 2,4-dimethylpyridine,        2,5-dimethylpyridine, 2,6-dimethylpyridine,        3,4-dimethylpyridine, 3,5-dimethylpyridine,        2,6-di-t-butylpyridine, 2,4-di-t-butylpyridine,        2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine,        pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl        ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran,        benzophenone, triphenylphosphine oxide, triphenyl phosphate or        phosphines or phosphites of formula PR₃, where R is        independently selected from methyl, ethyl, (C₃-C₆)alkyl,        substituted or unsubstituted (C₃-C₇)cycloalkyl, (C₆-C₁₀)aryl,        (C₆-C₁₀)aralkyl, methoxy, ethoxy, (C₃-C₆)alkoxy, substituted or        unsubstituted (C₃-C₇)cycloalkoxy, (C₆-C₁₀)aryloxy or        (C₆-C₁₀)arylalkoxy. Representative examples of PR₃ include        without any limitation trimethyl phosphine, triethyl phosphine,        tri-n-propyl phosphine, tri-iso-propyl phosphine, tri-n-butyl        phosphine, tri-iso-butyl phosphine, tri-tert-butyl phosphine,        tricyclopentylphosphine, triallylphosphine,        tricyclohexylphosphine, triphenyl phosphine, trimethyl        phosphite, triethyl phosphite, trifluoroethyl phosphite,        tri-n-propyl phosphite, tri-iso-propyl phosphite, tri-n-butyl        phosphite, tri-iso-butyl phosphite, tri-tert-butyl phosphite,        tricyclopentyiphosphite, triallylphosphite,        tricyclohexylphosphite, triphenyl phosphite, and the like. It        should however be noted that various other known LBs which will        bring about the intended activity can also be used in this        embodiment of the invention.

Various olefinic monomers which undergo vinyl addition polymerizationcan be employed in the composition of this invention. Such olefinicmonomers include without any limitation alicyclic olefins, such asethylene, propylene, butylene, styrene, and the like. Other olefinicmonomers include cyclo-olefins and bicyclo-olefins, and so on.

In some embodiments of this invention the olefinic monomers which aresuitable in the composition of this invention are of the formula (V),wherein:

m=0 or 1;

is a single bond;

at least one of R₁₃, R₁₄, R₁₅ and R₁₆ is selected from the groupconsisting of n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl,phenylbutyl, phenoxyethyl, biphenyloxyethyl and biphenyloxybutyl.

The monomers of formula (V) as described herein are themselves known inthe literature or can be prepared by any of the known methods in the artto make such or similar types of monomers.

In addition, the monomers as described herein readily undergo mass vinyladdition polymerization, i.e., in their neat form without use of anysolvents by vinyl addition polymerization using transition metalprocatalysts, such as for example, organopalladium compounds asdescribed herein. See for example, U.S. Pat. Nos. 7,442,800 B2; and7,759,439 B2; pertinent portions of which are incorporated herein byreference. The term “mass polymerization” as used herein shall have thegenerally accepted meaning in the art. That is, a polymerizationreaction that is generally carried out substantially in the absence of asolvent. In some cases, however, a small proportion of solvent ispresent in the reaction medium. For example, such small amounts ofsolvent may be used to dissolve the organopalladium compound of formulae(III), (IIIA) or (IIIB), and a photoacid generator or photosensitizer asdescribed herein or convey the same to the reaction medium. Also, somesolvent may be used to reduce the viscosity of the monomer. The amountof solvent that can be used in the reaction medium may be in the rangeof 0 to 5 weight percent based on the total weight of the monomersemployed. Any of the suitable solvents that dissolves theorganopalladium compound of formulae (III), (IIIA) or (IIIB), aphotoacid generator or photosensitizer and/or monomers can be employedin this invention. Examples of such solvents include alkanes,cycloalkanes, aromatics, such as toluene, ester solvents such as ethylacetate, THF, dichloromethane, dichloroethane, and the like.

Advantageously, it has now been found that one or more of the monomersthemselves can be used to dissolve the organopalladium compound offormulae (III), (IIIA) or (IIIB) or a photoacid generator orphotosensitizer and thus avoiding the need for the use of solvents. Inaddition, one monomer can itself serve as a solvent for the othermonomer and thus eliminating the need for an additional solvent. Forexample, if a first monomer of formula (V) is a solid at roomtemperature, then a second monomer of formula (V), which is a liquid atroom temperature can be used as a solvent for the first monomer offormula (V) which is a solid or vice versa. Therefore, in suchsituations more than one monomer can be employed in the composition ofthis invention.

In some embodiments, the monomers of formula (V) employed in thecomposition of this invention may serve as high refractive indexmaterials imparting high refractive index to the resulting polymericfilm upon mass polymerization. In general, the monomers of formula (V)which are suitable in this invention feature a refractive index of atleast 1.5. In some embodiments the refractive index of the monomers offormula (V) is higher than 1.5. In some other embodiments the refractiveindex of the monomers of formula (V) is in the range from about 1.5 to1.6. In yet some other embodiments the refractive index of the monomersof formula (V) is higher than 1.55, higher than 1.6 or higher than 1.65.In some other embodiments it may even be higher than 1.7.

In some other embodiments, it is generally contemplated that monomer offormula (V) may also be used as a viscosity modifier. Accordingly, ingeneral, such a monomer of formula (V) is a liquid at room temperatureand can be used in conjunction with another monomer of formula (V) whichis a solid or a high viscosity liquid.

In a further embodiment of this invention the composition of thisinvention encompasses at least two different monomers of formula (V) andis in a clear liquid state having a viscosity below 100 centipoise. Ingeneral, the composition of this invention exhibits low viscosity, whichcan be below 100 centipoise. In some embodiments, the viscosity of thecomposition of this invention is less than 90 centipoise. In some otherembodiments the viscosity of the composition of this invention is in therange from about 10 to 100 centipoise. In yet some other embodiments theviscosity of the composition of this invention is lower than 80 cP,lower than 60 cP, lower than 40 cP, lower than 20 cP. In some otherembodiments it may even be lower than 20 cP.

When the composition of this invention contains two monomers, they canbe present in any desirable amounts that would bring about the intendedbenefit, including either refractive index modification or viscositymodification or both or any other desirable property depending upon theintended final application. Accordingly, the molar ratio of firstmonomer of formula (V) to second monomer of formula (V) can be from0:100 to 100:0. That is, only one monomer of formula (V) can be employedin certain applications. In other words, any amount of these twomonomers can be employed. In some embodiments, the molar ratio of firstmonomer of formula (V):second monomer of formula (V) is in the rangefrom 1:99 to 99:1; in some other embodiments it is from 5:95 to 95:5; itis from 10:90 to 90:10; it is from 20:80 to 80:20; it is from 30:70 to70:30; it is from 60:40 to 40:60; and it is 50:50, and so on.

In general, the compositions in accordance with the present inventionencompass the above described one or more of monomer of formula (V), asit will be seen below, various composition embodiments are selected toprovide properties to such embodiments that are appropriate anddesirable for the use for which such embodiments are directed, thus suchembodiments are tailorable to a variety of specific applications.Accordingly, in some embodiments the composition of this inventioncontains more than two distinct monomers of formula (V), such as forexample three different monomers of formula (V) or four differentmonomers of formula (V).

For example, as already discussed above, proper combination of differentmonomers of formula (V) makes it possible to tailor a composition havingthe desirable refractive index, viscosity and optical transmissionproperties, among other properties. In addition, it may be desirable toinclude other polymeric or monomeric materials which are compatible toprovide desirable optical properties depending upon the end useapplication. Accordingly, the compositions of this invention can alsoinclude other high refractive polymeric materials which will bring aboutsuch intended benefit. Examples of such polymers include without anylimitation, poly(α-methylstyrene), poly(vinyl-toluene), copolymers ofα-methylstyrene and vinyl-toluene, and the like.

Advantageously, it has further been found that the compositions of thisinvention can also contain additional monomers different from themonomer of formula (V). In some embodiments, the composition accordingto this invention may further contain one or more monomers selected frommonomer of formula (VI) or monomer of formula (VII).

The monomer of formula (VI) is:

wherein:

o is an integer from 0 to 2, inclusive;

D is SiR₂₉R₃₀R₃₁ or a group selected from:—(CH₂)_(c)—O—SiR₂₉R₃₀R₃₁  (E);—(CH₂)_(c)—SiR₂₉R₃₀R₃₁  (F); and—(SiR₂₉R₃₀)_(c)—O—SiR₂₉R₃₀R₃₁  (G); wherein

c is an integer from 1 to 10, inclusive, and where one or more of CH₂ isoptionally substituted with (C₁-C₁₀)alkyl or (C₁-C₁₀)perfluoroalkyl;

R₂₆, R₂₇ and R₂₈ are the same or different and independently of eachother selected from hydrogen, halogen and hydrocarbyl, where hydrocarbylis selected from methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl or (C₆-C₁₀)aryloxy; and

R₂₉, R₃₀ and R₃₁ are each independently of one another methyl, ethyl,linear or branched (C₃-C₉)alkyl, substituted or unsubstituted(C₆-C₁₄)aryl, methoxy ethoxy, linear or branched (C₃-C₉)alkoxy orsubstituted or unsubstituted (C₆-C₁₄)aryloxy.

In this aspect of the invention, it has now been found that monomers offormula (VI) provides further advantages. Namely, the monomers offormula (VI) depending upon the nature of the monomer may impart high orlow refractive index to the composition, thus it can be tailored to meetthe need. In addition, the monomers of formula (VI) generally improvethe adhesion properties and thus can be used as “adhesion modifiers.”Finally, the monomers of formula (VI) may exhibit low viscosity and goodsolubility for the procatalyst and/or activator, among various otheradvantages.

The monomer of formula (VII) is:

wherein:

Z₁ is selected from the group consisting of substituted or unsubstituted(C₁-C₁₂)alkylene, —(CH₂)_(d)O(CH₂)_(e)—,—(CH₂)_(d)(SiR₃₈R₃₉)(OSiR₄₀R₄₁)_(f)(CH₂)_(e)— where d, e and f areindependently integers from 0 to 6, inclusive, R₃₈, R₃₉, R₄₀ and R₄₁ arethe same or different and independently of each other selected frommethyl, ethyl, linear or branched (C₃-C₁₂)alkyl, and an arylene selectedfrom the following:

R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are the same or different andindependently of each other selected from hydrogen, halogen andhydrocarbyl, where hydrocarbyl is selected from methyl, ethyl, linear orbranched (C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl or (C₆-C₁₀)-aryloxy.

The monomers of formula (VII) are bifunctional monomers and may exhibithigh refractive index especially when Z₁ is an arylene group.Accordingly, it is contemplated that incorporation of monomers offormula (VII) into composition of this invention generally increases therefractive index of the composition and also increase crosslinkabilitywith other molecules. Thus, by incorporation of monomers of formula(VII) into the composition of this invention it may be possible toincrease compatibility with other materials depending upon the intendedapplication thereby enhancing the properties of the composition of theinvention.

In another aspect of this invention it is conceivable that thecomposition of this invention may contain only one monomer of formula(V) or formula (VI) or formula (VII). That is, any one of the monomersof formulae (V) to (VII) may be sufficient to form a composition of thisinvention. In some other embodiments the composition of this inventionencompasses any two monomers of formulae (V) to (VII) and in anydesirable proportions. In some other embodiments the composition of thisinvention encompasses any three monomers of formulae (V) to (VII) in anycombinations thereof and in any desirable proportions. All such possiblepermutations and combinations of monomers of formulae (V) to (VII) arepart of this invention.

Accordingly, any of the monomers within the scope of monomer of formula(V) can be employed in the composition of the invention. Representativeexamples of monomer of formula (V) include the following without anylimitations:

Turning now to monomer of formula (VI) to form the composition of thisinvention it is contemplated that any monomer within the scope ofmonomer of formula (VI) can be employed. Exemplary monomers of such typeinclude but not limited to those selected from the group consisting of

Turning now to monomer of formula (VII) to form the composition of thisinvention it is contemplated that any monomer within the scope ofmonomer of formula (VII) can be employed. Exemplary monomers of suchtype include but not limited to those selected from the group consistingof:

In a further embodiment, the composition of this invention encompassesone or more monomers of formula (V) and at least one monomer of formula(VI).

In another embodiment, the composition of this invention encompasses oneor more monomers of formula (VI) and at least one monomer of formula(VII) and optionally one monomer of formula (V).

In yet a further embodiment, the composition of this inventionencompasses at least one monomer of formula (V) and at least one monomerof formula (VI), and optionally one monomer of formula (VII).

In yet a further embodiment, the composition of this inventionencompasses one monomer of formula (VI), optionally one or more monomersof formula (V) or monomer of formula (VII).

In yet another embodiment, the composition of this invention may includeone or more monomers selected from the following:

In a further embodiment of this invention, the composition contains anyof the organopalladium compounds of formulae (III), (IIIA) or (IIIB)that would bring about the mass polymerization as described herein.Generally, such suitable organopalladium compounds of formulae (III),(IIIA) or (IIIB) contain a bidentate monoanionic ligand which isselected from the group consisting of:

Several of the organopalladium compounds of formula (I) that aresuitable to be employed in the compositions of this invention are knownin the literature or can be readily made by any of the known proceduresin the art. See for example, U.S. Pat. Nos. 7,442,800 B2 and 7,759,439B2, pertinent portions of which are incorporated herein by reference.

Exemplary organopalladium compounds of formulae (III), (IIIA) or (IIIB)that can be employed in the composition of this invention without anylimitation include the following:

As noted, the composition of this invention further contains a solublephotoacid generator which when combined with the organopalladiumcompound of formulae (III), (IIIA) or (MB) and a photosensitizer willcause mass polymerization of the monomers contained therein when exposedto suitable radiation as described herein. Any of the known photoacidgenerators can be used in the compositions of this invention, whichwould being about this effect, such as for example, certain of thehalonium salts, sulfonium salts, and the like.

In some embodiments the soluble photoacid generator of the formula(I_(a)) are employed in the composition of this invention:Aryl₁-Hal^(⊕)-Aryl₂ An^(⊖)  (I_(a))Wherein Aryl₁ and Aryl₂ are the same or different and are independentlyselected from the group consisting of substituted or unsubstitutedphenyl, biphenyl and naphthyl; Hal is iodine or bromine; and An^(⊖) is aweakly coordinating anion (WCA) which is weakly coordinated to thecation complex. More specifically, the WCA anion functions as astabilizing anion to the cation complex. The WCA anion is relativelyinert in that it is non-oxidative, non-reducing, and non-nucleophilic.In general, the WCA can be selected from borates, phosphates, arsenates,antimonates, aluminates, boratobenzene anions, carborane, halocarboraneanions, sulfonamidate, sulfonates,tris(perfluoro(C₁-C₄)alkanesulfonyl)methide andbis(perfluoro-(C₁-C₄)alkanesulfonyl)imide.

Representative examples of the compounds of formula (I_(a)) may belisted as follows:

Wherein R₁₁ and R₁₂ are as defined herein. Similarly various sulfoniumsalts can be used as photoacid generators, which include broadlycompounds of formula (II) as described herein.

Accordingly, non-limiting examples of suitable photoacid generators offormulae (I) or (II) that may be employed in the composition of thisinvention are listed below:

where R₄₂ and R₄₃ are the same or different and each independentlyselected from linear or branched (C₁₀-C₁₃)alkyl, for example iodonium,diphenyl-, 4,4′-di-C₁₀₋₁₃-alkylphenyl derivatives,tetrakis(2,3,4,5,6-pentafluorophenyl)borates are commercially availableunder the tradename SILCOLEASE UV CATA 243;

However, any of the other known photoacid generators which can activatethe organopalladium compounds of formulae (III), (IIIA) or (MB) asemployed herein when exposed to suitable radiation can also be used inthe composition of this invention. All such compounds are part of thisinvention.

As noted, the composition of this invention additionally contains aphotosensitizer compound which further facilitates the formation of theactive catalyst when the composition is exposed to suitable radiation inthe presence of the photoacid generator as employed herein. For thispurpose, any suitable sensitizer compound can be employed in thecompositions of the present invention, which activates the photoacidgenerator and/or the organopalladium compound of formulae (III), (IIIA)or Such suitable sensitizer compounds include, anthracenes,phenanthrenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes,xanthones, indanthrenes, thioxanthen-9-ones, and mixtures thereof. Insome exemplary embodiments, suitable sensitizer components include acompound of formula (VIII) or a compound of formula (IX):

wherein

R₄₄, R₄₅ and R₄₆ are the same or different and independently of eachother selected from the group consisting of hydrogen, halogen, hydroxy,NO₂, NH₂, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₆-C₁₀)-aryloxy, C(O)(C₁-C₆)alkyl, COOH,C(O)O(C₁-C₆)alkyl, and SO₂(C₆-C₁₀)aryl;

R₄₇ and R₄₈ are the same or different and independently of each otherselected from the group consisting of methyl, ethyl, linear or branched(C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl and (C₆-C₁₀)aryl(C₁-C₃)alkyl.

Representative examples of the compounds of formula (VIII) or thecompounds of formula (IX) without any limitation may be listed asfollows:

Other suitable photosensitizer compounds include various substituted andunsubstituted phenothiazine derivatives, such as for example:

Generally, photosensitizers absorb energy from the radiated light sourceand transfers that energy to the desirable substrate/reactant, which inthe present invention is the photoacid generator employed in thecomposition of this invention. In some embodiments the compounds offormula (VIII) or the compounds of formula (IX) can be activated atcertain wavelength of the electromagnetic radiation which can generallyrange from about 240 nm to 410 nm. Accordingly, any of the compoundswhich are active in this electromagnetic radiation can be employed inthe compositions of this invention which are stable to variousfabrications methods where the compositions of this invention can beused including for example OLED or the 3D fabrication methods. In someembodiments the wavelength of the radiation to activate the compounds offormulae (VIII) or (IX) is 260 nm. In some other embodiments thewavelength of the radiation to activate the compounds of formula (VIII)or (IX) is 310 nm. In some other embodiments the wavelength of theradiation to activate the compounds of formula (VIII) or (IX) is 365 nm.In yet some other embodiments the wavelength of the radiation toactivate the compounds of formula (VIII) or (IX) is 395 nm.

Any amount of organopalladium compound of formulae (III), (IIIA) or(IIIB), the photoacid generator of formulae (I) or (II) and thephotosensitizer of formulae (VIII) or (IX) can be employed in thecomposition of this invention which will bring about the intendedresult. Generally, the molar ratio of monomer of formula (V):compound offormulae (III), (IIIA) or (IIIB) is in the range of 25,000:1 to 5,000:1or lower. In some other embodiments such monomer of formula (V):compoundof formula (I) is 10,000:1, 15,000:1, 20,000:1 or higher than 30,000:1.It should be noted that monomer of formula (V) as mentioned herein mayinclude one or more monomers of formula (V) distinct from each other andmay additionally contain one or more monomers of formulae (VI) or (VII),and therefore, the above ratio represents combined molar amounts of allsuch monomers employed. Similarly, the molar ratio of organopalladiumcompound of formulae (III), (IIIA) or (IIIB):the photoacid generator offormulae (I) or (II):the photosensitizer of formulae (VIII) or (IX) isin the range of 1:1:0.5 to 1:2:2 or 1:2:1 or 1:4:1, 1:2:4, 1:1:2, 1:4:2or such ranges which will bring about the intended benefit.

Advantageously, it has further been found that the composition accordingto this invention forms a substantially transparent film when exposed toa suitable actinic radiation (UV irradiation). That is to say that whenthe composition of this invention is exposed to certain actinicradiation, the monomers undergo mass polymerization to form films whichare substantially transparent to visible light. That is, most of thevisible light is transmitted through the film. In some embodiments suchfilm formed from the composition of this invention exhibits atransmission of equal to or higher than 90 percent of the visible light.In some other embodiments such film formed from the composition of thisinvention exhibits a transmission of equal to or higher than 95 percentof the visible light. It should be further noted that any actinicradiation that is suitable to carry out this mass polymerization can beemployed, such as for example, exposure to any actinic radiation in thewavelength of 200 nm to 400 nm. However, any radiation higher than 400nm can also be employed. In some embodiments the wave length of theactinic radiation employed is 250 nm, 295 nm, 360 nm, 395 nm or higherthan 400 nm.

In some other embodiments the composition of this invention undergoesmass polymerization when exposed to suitable actinic radiation and heatto form a substantially transparent film. In yet other embodiments thecomposition of this invention undergoes mass polymerization when exposedto suitable UV irradiation at a temperature from 50° C. to 100° C. toform a substantially transparent film.

Accordingly, exemplary compositions of this invention without anylimitation may be enumerated as follows:

5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB), palladiumhexafluoroacetylacetonate (Pd520), 4,4′-di-C₁₀₋₁₃-alkylphenylderivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borates (PAG1) and2-isopropyl-9H-thioxanthen-9-one (ITX);

5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB),5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtOPhPh), palladium hexafluoroacetylacetonate (Pd520),4,4′-di-C₁₀₋₁₃-alkylphenyl derivatives,tetrakis(2,3,4,5,6-pentafluorophenyl)borates (PAG1) and2-isopropyl-9H-thioxanthen-9-one (ITX);

5-decylbicyclo[2.2.1]hept-2-ene (DecNB),5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtOPhPh), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II)(Pd472), bis(4-n-dodecylphenyl)iodoniumtetrakis(pentafluorophenyl)borate (PAG2) and2-chloro-9H-thioxanthen-9-one (CTX);

5-decylbicyclo[2.2.1]hept-2-ene (DecNB),bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II) (Pd472),di(4-n-dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate (PAG2)and 2-chloro-9H-thioxanthen-9-one (CTX); and

5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB), palladiumhexafluoroacetylacetonate (Pd520), di(4-n-dodecylphenyl)iodoniumtetrakis(pentafluorophenyl)borate (PAG2) and2-isopropyl-9H-thioxanthen-9-one (ITX).

In a further aspect of this invention there is provided a kit forforming a substantially transparent film. There is dispensed in this kita composition of this invention. Accordingly, in some embodiments thereis provided a kit in which there is dispensed one or more olefinicmonomers of formula (V) as described herein; an organopalladium compoundof formula (III) or an organopalladium compound of formula (IIIA) or anorganopalladium compound of formula (IIIB) as described herein; aphotoacid generator of formulae (I) or (II) as described herein and aphotosensitizer of formulae (VIII) or (IX). In some embodiments the kitof this invention contains one or more monomers of formula (V)optionally in combination with one or more monomers of formulae (VI) or(VII) so as to obtain a desirable result and/or for an intended purpose.

In some embodiments, the aforementioned kit encompasses one or moremonomers of formula (V) and one or more monomers of formulae (VI) or(VII). In some other embodiments the kit of this invention encompassesat least two monomers wherein first monomer serves as a solvent for thesecond monomer. Any of the monomers of formulae (V) to (VII) asdescribed herein can be used in this embodiment. The molar ratio of suchtwo monomers contained in these embodiments can vary and may range from1:99 to 99:1, or 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 60:40to 40:60 or 50:50, and so on. In some other embodiments the kit mayencompass a composition wherein dispensed two monomers which could beone monomer of formula (V) and another monomer of formula (VI). Further,the monomer of formula (VI) is completely soluble in monomer of formula(V) to form a clear solution at room temperature. In some embodimentsthe monomer mixture may become a clear solution at slightly elevatedtemperature, such as for example, 30° C. or 40° C. or 50° C., beforethey undergo mass polymerization.

In another aspect of this embodiment of this invention the kit of thisinvention undergoes mass polymerization when exposed to suitable actinicradiation for a sufficient length of time to form a polymeric film. Thatis to say that the composition of this invention is poured onto asurface or onto a substrate which needs to be encapsulated and exposedto suitable radiation in order for the monomers to undergopolymerization to form a solid transparent polymer which could be in theform of a transparent film. Generally, as already noted above, suchpolymerization can take place at various wavelengths of actinicradiation, such as for example, at 265 nm 315 nm 365 nm or 395 nm and soon. The mass polymerization may further be accelerated by heating, whichcan also be in stages, for example heating to 40° C. or 50° C. or 60° C.for 5 minutes each, and if necessary further heating to 70° C. forvarious lengths of time such as from 5 minutes to 15 minutes and so on.By practice of this invention it is now possible to obtain polymericfilms on such substrates which are substantially transparent film. The“substantially transparent film” as used herein means that the filmsformed from the composition of this invention are optically clear in thevisible light. Accordingly, in some embodiments of this invention suchfilms are having at least 90 percent of visible light transmission, insome other embodiments the films formed from the composition of thisinvention exhibit at least 95 percent of visible light transmission.

In some embodiments of this invention the kit as described hereinencompasses a composition which further contains one or more monomersselected from a monomer of formula (VI) or a monomer of formula (VII) asdescribed hereinabove. Again, any of the monomers of formula (VI) or(VII) as described herein can be used in this embodiment, and in anydesirable amounts depending on the nature of the intended use.

In some embodiments, the kit as described herein encompasses variousexemplary compositions as described hereinabove.

In yet another aspect of this invention there is further provided amethod for forming a substantially transparent film for the fabricationof a variety of optoelectronic device comprising:

forming a homogeneous clear composition comprising one or more monomersof formula (V); an organopalladium compound of formula (III) or anorganopalladium compound of formula (IIIA) or an organopalladiumcompound of formula (MB); a photoacid generator of formulae (I) or (II);and a photosensitizer of formulae (VIII) or (IX);

coating a suitable substrate with the composition or pouring thecomposition onto a suitable substrate to form a film; and

exposing the film to a suitable actinic radiation to causepolymerization of the monomers.

The coating of the desired substrate to form a film with the compositionof this invention can be performed by any of the coating procedures asdescribed herein and/or known to one skilled in the art, such as by spincoating. Other suitable coating methods include without any limitationspraying, doctor blading, meniscus coating, ink jet coating and slotcoating. The mixture can also be poured onto a substrate to form a film.Suitable substrate includes any appropriate substrate as is, or may beused for electrical, electronic or optoelectronic devices, for example,a semiconductor substrate, a ceramic substrate, a glass substrate.

Next, the coated substrate is exposed to suitable radiation as describedherein. Alternatively, the coated substrate is baked, i.e., heated tofacilitate the mass polymerization, for example to a temperature from50° C. to 100° C. for about 1 to 60 minutes, although other appropriatetemperatures and times can be used. In some embodiments the substrate isbaked at a temperature of from about 60° C. to about 90° C. for 2minutes to 10 minutes. In some other embodiments the substrate is bakedat a temperature of from about 60° C. to about 90° C. for 5 minutes to20 minutes.

The films thus formed are then evaluated for their optical propertiesusing any of the methods known in the art. For example, the refractiveindex of the film across the visible spectrum can be measured byellipsometry. The optical quality of the film can be determined byvisual observation. Quantitatively the percent transparency can bemeasured by visible spectroscopy. Generally, the films formed accordingto this invention exhibit excellent optical transparent properties andcan be tailored to desirable refractive index as described herein.

Accordingly, in some of the embodiments of this invention there is alsoprovided an optically transparent film obtained by the masspolymerization of the composition as described herein. In anotherembodiment there is also provided an optoelectronic device comprisingthe transparent film of this invention as described herein.

In yet some other embodiments the composition of this invention can alsobe used in a variety of photo induced nanoimprint lithography (NIL),such as for example, UV-NIL. For instance, the compositions of thisinvention can be used in a variety of photocurable imprint technology.Typically in such applications, the composition of this invention issuitably placed on a substrate (for example by coating or similarmeans), which is then covered by a suitable stamp and exposed toradiation so as to allow the composition of this invention to cure to asolid. The stamp is then released to obtain the nano-imprinted film.Such substrates can include for example a master digital video disk(DVD).

The following examples are detailed descriptions of methods ofpreparation and use of certain compounds/monomers, polymers andcompositions of the present invention. The detailed preparations fallwithin the scope of, and serve to exemplify, the more generallydescribed methods of preparation set forth above. The examples arepresented for illustrative purposes only, and are not intended as arestriction on the scope of the invention. As used in the examples andthroughout the specification the ratio of monomer to catalyst is basedon a mole to mole basis.

EXAMPLES

The following abbreviations have been used hereinbefore and hereafter indescribing some of the compounds, instruments and/or methods employed toillustrate certain of the embodiments of this invention:

NBEtOPhPh—5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene;HexylNB—5-hexylbicyclo[2.2.1]hept-2-ene; Pd520—palladiumhexafluoroacetylacetonate;Pd472—-bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II);Rhodorsil PI 2074—tolylcumyliodonium-tetrakis pentafluorophenylborate;PAG1—4,4′-di-C₁₀₋₁₃-alkylphenyl derivatives,tetrakis(2,3,4,5,6-pentafluorophenyl)borates;PAG2—bis(4-n-dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate;PAG3—di(dodecylphenyl)iodonium bis(trifluoromethane)sulfonimide;Rhodorsil 2074®—tolylcumyliodonium-tetrakis pentafluorophenylborate;ITX—4-isopropylthioxanthone; CTX—4-chlorothioxanthone;DCM—dichloromethane; cP—centipoise; DSC—differential scanningcalorimetry.

Various monomers as used herein are either commercially available or canbe readily prepared following the procedures as described in U.S. Pat.No. 9,944,818.

Various organopalladium compounds of formula (I) as used herein areknown in the literature and can be readily prepared following theprocedures as described in the literature. Various photoacid generatorsas used herein are either available commercially or can be readilyprepared following the procedures as described hereinbelow in Examples Ato C.

Example A Bis(4-n-dodecylphenyl)iodoniumtetrakis(pentafluorophenyl)borate (PAG2)

In a suitable reaction vessel equipped with a magnetic stirrer wasplaced a mixture of 1-phenyldodecane (34.5 g, 140 mmol), potassiumperiodate (15 g, 70 mmol), acetic anhydride (30 g, 294 mmol) and aceticacid (10 g). The reaction mixture was cooled with an ice bath. To thissolution carefully was added dropwise a solution of sulfuric acid (16 g)dissolved in acetic anhydride (20 g). After the addition, reactionmixture was stirred overnight. Then, water (20 ml) was added followed byan aqueous solution of NaCl (10.2 g, 170 mmol dissolved in 50 ml ofwater). The reaction mixture was cooled to 0° C. and the resultingprecipitate was collected.

The precipitate was then washed with cold isopropanol and methanol andair dried overnight to obtain di(p-dodecylphenyl)iodonium chloride (13g, 31% yield). The precipitate thus obtained was then dispersed indichloromethane (5 ml) and to this was added lithiumtetrakis(pentafluorophenyl)borate dissolved in dichloromethane (20 ml).The mixture was stirred for 30 minutes and an additional 50 ml ofdichloromethane was added. The reaction mixture was filtered using a0.45 μm PTFE filter. Removed solvent in vacuo to obtainbis(4-n-dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate (PAG2,18.4 g 70% yield).

Example B Bis(4-dodecylphenyl)iodoniumtetrakis((1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl)oxy)aluminate

In a suitable reaction vessel was placed di(dodecylphenyl)iodoniumchloride (0.67 g, 1.03 mmol) dispersed in dichloromethane (˜5 ml). Thisdispersion was added in 1 ml increments to a solution of lithiumtetrakis(perfluoro-tert-butoxy) aluminate (1 g, 1.03 mmol) dissolved ina mixture of acetone (2 ml) and dichloromethane (25 ml). The resultingmixture was stirred for 25 minutes then filtered through a 5 μm nylonsyringe filter. After filtering, the solvent was removed in vacuo andthe residue was re-dissolved in dichloromethane (5 ml). This solutionwas filtered through a 5 μm nylon syringe filter. After filtering, thesolvent was removed in vacuo to obtain the tile compound: 1.53 g (94%yield)

Example C Di(dodecylphenyl)iodonium Bis(trifluoromethane)sulfonimide

In a suitable reaction vessel was dispersed didodecylphenyliodoniumchloride (1 g, 1.53 mmol) in 5 ml of DCM. To this dispersion was added asolution of lithium bis(trifluoromethane)sulfonimide (0.44 g, 1.53 mmol)dissolved in 5 ml of a 1:1 mixture of DCM and ethyl acetate. After thelithium bis(trifluoromethane)sulfonimide addition, the reaction mixturewas stirred for an additional 30 minutes and then an additional 15 ml ofDCM was added to the mixture. The reaction mixture was filtered using a0.45 μm PTFE syringe filter and the solvent was removed in vacuo. Theresulting residue was redissolved in DCM and filtered again through 0.45μm PTFE syringe filter. The DCM was removed in vacuo to give 1.19 g(86%) of di(dodecylphenyl)iodonium bis(trifluoromethane)sulfonimide(PAG3).

The following Examples 1 to 5 demonstrate the benefits obtained by thesoluble photoacid generators in accordance with this invention.

Example 1 Mass Polymerization of HexylNB with Pd800

In a glass bottle, Pd520(1 molar part), PAG1 (3 molar parts), ITX (1molar part) were dissolved in HexylNB (4000 molar parts) undersonication to form a clear solution. This solution was then UV lightexposed for 4 sec (2 J/cm², 395 nm) at room temperature. The solutionturned into a film indicating the monomer was polymerized, as alsoconfirmed by UV-DSC.

Example 2

The procedures of Example 1 were substantially followed in this Example2 except for using 4500 molar parts of HexylNB and 4 molar parts ofPAG1. The solution turned into film upon exposure to UV light for 4 sec(2 J/cm², 395 nm) at room temperature.

Example 3

The procedures of Example 1 were substantially followed in this Example3 except for using 4500 molar parts of HexylNB, 500 molar parts ofNBEtOPhPh and 4 molar parts of PAG1. The solution turned into film uponexposure to UV light for 4 sec (2 J/cm², 395 nm) at room temperature.

Example 4

The procedures of Example 1 were substantially followed in this Example4 except for using 5000 molar parts of HexylNB and 5 molar parts ofPAG1. The heat of reaction as measured by UV-DSC was about 356 J/g.

Example 5

The procedures of Example 1 were substantially followed in this Example5 except for using 5000 molar parts of HexylNB and 5 molar parts ofPAG2. The heat of reaction as measured by UV-DSC was about 316 J/g.

The following Comparative Examples 1-2 demonstrate that use of otherreadily available iodonium salts, such as for example, Rhodorsil 2074®as the photoacid generator results in no polymerization of the monomers.

Comparative Example 1

The procedures of Example 1 were substantially followed in thisComparative Example 1 except for using 4 molar parts of Rhodorsil 2074.Rhodorsil 2074 was not completely miscible in HexylNB. No reaction wasobserved upon exposure to UV light for 4 sec (2 J/cm², 395 nm) at roomtemperature as evidenced by the reaction mixture remained in the liquidform. The UV-DSC of a portion of the sample further confirmed formationof no exotherm at elevated temperatures.

Comparative Example 2

The procedures of Example 3 were substantially followed in thisComparative

Example 2 except for using 4 molar parts of Rhodorsil 2074. Rhodorsil2074 was not completely miscible in the monomeric mixture. No reactionwas observed upon exposure to UV light for 4 sec (2 J/cm², 395 nm) atroom temperature as evidenced by the reaction mixture remained in theliquid form. The UV-DSC of a portion of the sample further confirmedformation of no exotherm at elevated temperatures.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A composition comprising: a) a soluble photoacidgenerator selected from the group consisting of a compound of formula(I):

and a compound of formula (II):

wherein: a is an integer from 1 to 5; An^(⊖) is selected from the groupconsisting of Cl^(⊖), Br^(⊖), I^(⊖), BF₄ ^(⊖),tetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,(triphenylsiloxy)tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate,tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]pheny-l]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate,PF₆ ^(⊖), SbF₆ ^(⊖), n-C₄F₉SO₃ ^(⊖), CF₃SO₃ ^(⊖) and p-CH₃(C₆H₄)—SO₃^(⊖); at least one of R₈, R₉, R₁₀, R₁₁ and R₁₂ is selected from thegroup consisting of linear or branched (C₁₀-C₂₀)alkyl,(C₆-C₁₀)aryl(C₁₀-C₂₀)alkyl, (C₁₀-C₂₀)alkoxy,(C₆-C₁₀)aryloxy(C₁₀-C₂₀)alkyl, (C₁₀-C₂₀)alkanoyl(C₆-C₁₀)aryl and(C₁₀-C₂₀)alkoxy(C₆-C₁₀)aroyl(C₆-C₂₀)alkyl; and the remaining R₈, R₉,R₁₀, R₁₁ and R₁₂ are the same or different and each independentlyselected from the group consisting of halogen, methyl, ethyl, linear orbranched (C₃-C₂₀)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₆-C₁₀)-aryloxy,(C₆-C₁₀)thioaryl, (C₁-C₆)alkanoyl(C₆-C₁₀)thioaryl,(C₁-C₆)alkoxy(C₆-C₁₀)aroyl(C₁-C₆)alkyl and(C₆-C₁₀)thioaryl-(C₆-C₁₀)diarylsulfonium salt; b) an organopalladiumcompound selected from the group consisting of a compound of formula(III), a compound of formula (IIIA) and a compound of formula (IIIB):

wherein: L is a ligand selected from the group consisting of P(R)₃,P(OR)₃, O═P(R)₃, RCN and substituted or unsubstituted pyridines, where Ris selected from the group consisting of methyl, ethyl, linear orbranched (C₃-C₁₆)alkyl, (C₁-C₁₆)perfluoroalkyl, (C₃-C₁₀)cycloalkyl,(C₆-C₁₀)aryl(C₁-C₁₆)alkyl and substituted or unsubstituted (C₆-C₁₀)aryl;each A independently is a bidentate monoanionic ligand of formula (IV):

wherein: n is an integer 0, 1 or 2; X and Y are independently of eachother selected from O, N and S; R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are thesame or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,(C₁-C₁₆)perfluoroalkyl, (C₃-C₁₀)cycloalkyl, (C₆-C₁₀)aryl(C₁-C₁₆)alkyland substituted or unsubstituted (C₆-C₁₀)aryl; provided when either X orY is O or S, R₁ and R₅, respectively, do not exist; c) one or moreolefinic monomers of the formula (V):

wherein: m is an integer 0, 1 or 2;

is a single bond or a double bond; at least one of R₁₃, R₁₄, R₁₅ and R₁₆is selected from the group consisting of linear or branched(C₆-C₁₆)alkyl, (C₆-C₁₂)aryl(C₁-C₁₆)alkyl, (C₆-C₁₀)aryloxy(C₂-C₁₆)alkyland (C₆-C₁₀)aryl(C₆-C₁₀)aryloxy(C₁-C₁₆)alkyl; the remaining R₁₃, R₁₄,R₁₅ and R₁₆ are the same or different and each independently selectedfrom the group consisting of hydrogen, halogen, a hydrocarbyl orhalohydrocarbyl group selected from methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy,

wherein: Z is selected from the group consisting of: O, CO, C(O)O,OC(O), OC(O)O, S, (CR₁₇R₁₈)_(b), O(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)O,C(O)(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)C(O), C(O)O(CR₁₇R₁₈)_(b),(CR₁₇R₁₈)_(b)C(O)O, OC(O)(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)OC(O),(CR₁₇R₁₈)_(b)OC(O)O, (CR₁₇R₁₈)_(b)OC(O)O(CR₁₇R₁₈)_(b),OC(O)O(CR₁₇R₁₈)_(b), S(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)S, (SiR₁₇R₁₈)_(b),O(SiR₁₇R₁₈)_(b), (SiR₁₇R₁₈)_(b)O, where R₁₇ and R₁₈ are the same ordifferent and each independently selected from hydrogen, methyl, ethyl,linear or branched (C₃-C₁₂)alkyl, substituted or unsubstituted(C₆-C₁₄)aryl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,(C₂-C₆)acyl, (C₂-C₆)acyloxy, and substituted or unsubstituted(C₆-C₁₄)aryloxy; and b is an integer from 0 to 12, inclusive; Aryl isselected from the group consisting of substituted or unsubstitutedphenyl, substituted or unsubstituted biphenyl and substituted orunsubstituted naphthyl, substituted or unsubstituted terphenyl,substituted or unsubstituted anthracenyl substituted or unsubstitutedfluorenyl, wherein said substituents are selected from the groupconsisting of halogen, methyl, ethyl, linear or branched (C₃-C₆)alkyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₀)aryloxy, (C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy andperfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy; k is an integer from 1 to 12; R₂₃,R₂₄ and R₂₅ are the same or different and each independently selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, methoxy, ethoxy, linear orbranched (C₃-C₁₂)alkoxy, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl,perfluoro(C₆-C₁₀)aryl and perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl; or R₂₃ andR₂₄ taken together with the intervening carbon atoms to which they areattached to form a substituted or unsubstituted (C₅-C₁₄)cyclic,(C₅-C₁₄)bicyclic or (C₅-C₁₄)tricyclic ring; and Arylene is substitutedor unsubstituted bivalent (C₆-C₁₄)aryl; or one of R₁₃ and R₁₄ takentogether with one of R₁₅ and R₁₆ and the carbon atoms to which they areattached to form a substituted or unsubstituted (C₅-C₁₄)cyclic,(C₅-C₁₄)bicyclic or (C₅-C₁₄)tricyclic ring; and m) a photosensitizer. 2.The composition according to claim 1, wherein said olefinic monomer offormula (V) is having: m=0 or 1;

is a single bond; at least one of R₁₃, R₁₄, R₁₅ and R₁₆ is selected fromthe group consisting of n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,n-dodecyl, phenylbutyl, phenoxyethyl, biphenyloxyethyl andbiphenyloxybutyl.
 3. The composition according to claim 1, wherein saidcomposition comprises at least two different monomers of formula (V) andis in a clear liquid state having a viscosity below 100 centipoise. 4.The composition according to claim 1, wherein said composition containssaid two distinctive monomers of formula (V) in a molar ratio of from1:99 to 99:1.
 5. The composition according to claim 1, wherein saidcomposition forms a substantially transparent film when exposed tosuitable actinic radiation.
 6. The composition according to claim 5,wherein said film has a transmission of equal to or higher than 90percent of the visible light.
 7. The composition according to claim 1,wherein said bidentate monoanionic ligand is selected from the groupconsisting of:


8. The composition according to claim 1 further comprising one or moremonomers selected from monomer of formula (VI) or monomer of formula(VII), wherein said monomer of formula (VI) is:

wherein: o is an integer from 0 to 2, inclusive; D is SiR₂₉R₃₀R₃₁ or agroup selected from:—(CH₂)_(c)—O—SiR₂₉R₃₀R₃₁  (E);—(CH₂)_(c)—SiR₂₉R₃₀R₃₁  (F); and—(SiR₂₉R₃₀)_(c)—O—SiR₂₉R₃₀R₃₁  (G); wherein c is an integer from 1 to10, inclusive, and where one or more of CH₂ is optionally substitutedwith (C₁-C₁₀)alkyl or (C₁-C₁₀)perfluoroalkyl; R₂₆, R₂₇ and R₂₈ are thesame or different and independently of each other selected fromhydrogen, halogen and hydrocarbyl, where hydrocarbyl is selected frommethyl, ethyl, linear or branched (C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl or (C₆-C₁₀)aryloxy; and R₂₉, R₃₀ and R₃₁ areeach independently of one another methyl, ethyl, linear or branched(C₃-C₉)alkyl, substituted or unsubstituted (C₆-C₁₀)aryl, methoxy ethoxy,linear or branched (C₃-C₉)alkoxy or substituted or unsubstituted(C₆-C₁₄)aryloxy; said monomer of formula (VII) is:

wherein: Z₁ is selected from the group consisting of substituted orunsubstituted (C₁-C₁₂)alkylene, —(CH₂)_(d)O(CH₂)_(e)—,—(CH₂)_(d)(SiR₃₈R₃₉)(OSiR₄₀R₄₁)_(f)(CH₂)_(e)— where d, e and f areindependently integers from 0 to 6, inclusive, R₃₈, R₃₉, R₄₀ and R₄₁ arethe same or different and independently of each other selected frommethyl, ethyl, linear or branched (C₃-C₁₂)alkyl, and an arylene selectedfrom the following:

R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are the same or different andindependently of each other selected from hydrogen, halogen andhydrocarbyl, where hydrocarbyl is selected from methyl, ethyl, linear orbranched (C₃-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl or (C₆-C₁₀)-aryloxy.9. The composition according to claim 1, wherein the monomer of formula(V) is selected from the group consisting of:


10. The composition according to claim 8, wherein the monomer of formula(VI) or the monomer of formula (VII) is selected from the groupconsisting of:


11. The composition according to claim 1, wherein the organopalladiumcompound of formula (III) or the organopalladium compound of formula(IIIA) or the organopalladium compound of formula (IIIB) is selectedfrom the group consisting of:


12. The composition according to claim 1, wherein the compound offormula (I) or the compound of formula (II) is selected from the groupconsisting of:


13. The composition according to claim 1, wherein the photosensitizer isa compound of formula (VIII) or a compound of formula (IX):

wherein R₄₄, R₄₅ and R₄₆ are the same or different and independently ofeach other selected from the group consisting of hydrogen, halogen,hydroxy, NO₂, NH₂, methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₆-C₁₀)-aryloxy, C(O)(C₁-C₆)alkyl, COOH,C(O)O(C₁-C₆)alkyl, and SO₂(C₆-C₁₀)aryl; R₄₇ and R₄₈ are the same ordifferent and independently of each other selected from the groupconsisting of methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl and (C₆-C₁₀)aryl(C₁-C₃)alkyl.
 14. The composition accordingto claim 1, wherein the compound of formula (VIII) or the compound offormula (IX) is selected from the group consisting of:


15. The composition according to claim 1, which is selected from thegroup consisting of: 5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB),palladium hexafluoroacetylacetonate (Pd520), 4,4′-di-C₁₀₋₁₃-alkylphenylderivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borates (PAG1) and2-isopropyl-9H-thioxanthen-9-one (ITX); 5-hexylbicyclo[2.2.1]hept-2-ene(HexylNB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtOPhPh), palladium hexafluoroacetylacetonate (Pd520),4,4′-di-C₁₀₋₁₃-alkylphenyl derivatives,tetrakis(2,3,4,5,6-pentafluorophenyl)borates (PAG1) and2-isopropyl-9H-thioxanthen-9-one (ITX); 5-decylbicyclo[2.2.1]hept-2-ene(DecNB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtOPhPh), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II)(Pd472), bis(4-n-dodecylphenyl)iodoniumtetrakis(pentafluorophenyl)borate (PAG2) and2-chloro-9H-thioxanthen-9-one (CTX); 5-decylbicyclo[2.2.1]hept-2-ene(DecNB), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II)(Pd472), di(4-n-dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate(PAG2) and 2-chloro-9H-thioxanthen-9-one (CTX); and5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB), palladiumhexafluoroacetylacetonate (Pd520), di(4-n-dodecylphenyl)iodoniumtetrakis(pentafluorophenyl)borate (PAG2) and2-isopropyl-9H-thioxanthen-9-one (ITX).
 16. A kit for forming asubstantially transparent film comprising: a) a soluble photoacidgenerator selected from the group consisting of a compound of formula(I):

and a compound of formula (II):

wherein: a is an integer from 1 to 5; An ^(⊖) is selected from the groupconsisting of Cl^(⊖), Br^(⊖), I^(⊖), BF₄ ^(⊖),tetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,(triphenylsiloxy)tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate,tetrads[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]pheny-l]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl)phenyl]borate,PF₆ ^(⊖), SbF₆ ^(⊖), n-C₄F₉SO₃ ^(⊖), CF₃SO₃ ^(⊖) and p-CH₃(C₆H₄)—SO₃^(⊖); at least one of R₈, R₉, R₁₀, R₁₁ and R₁₂ is selected from thegroup consisting of linear or branched (C₁₀-C₂₀)alkyl,(C₆-C₁₀)aryl(C₁₀-C₂₀)alkyl, (C₁₀-C₂₀)alkoxy,(C₆-C₁₀)aryloxy(C₁₀-C₂₀)alkyl, (C₁₀-C₂₀)alkanoyl(C₆-C₁₀)aryl and(C₁₀-C₂₀)alkoxy(C₆-C₁₀)aroyl(C₆-C₂₀)alkyl; and the remaining R₈, R₉,R₁₀, R₁₁ and R₁₂ are the same or different and each independentlyselected from the group consisting of halogen, methyl, ethyl, linear orbranched (C₃-C₂₀)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₆-C₁₀)-aryloxy,(C₆-C₁₀)thioaryl, (C₁-C₆)alkanoyl(C₆-C₁₀)thioaryl,(C₁-C₆)alkoxy(C₆-C₁₀)aroyl(C₁-C₆)alkyl and(C₆-C₁₀)thioaryl-(C₆-C₁₀)diarylsulfonium salt; b) an organopalladiumcompound selected from the group consisting of a compound of formula(III), a compound of formula (IIIA) and a compound of formula (IIIB):

wherein: L is a ligand selected from the group consisting of P(R)₃,P(OR)₃, O═P(R)₃, RCN and substituted or unsubstituted pyridines, where Ris selected from the group consisting of methyl, ethyl, linear orbranched (C₃-C₁₆)alkyl, (C₁-C₁₆)perfluoroalkyl, (C₃-C₁₀)cycloalkyl,(C₆-C₁₀)aryl(C₁-C₁₆)alkyl and substituted or unsubstituted (C₆-C₁₀)aryl;each A independently is a bidentate monoanionic ligand of formula (IV):

wherein: n is an integer 0, 1 or 2; X and Y are independently of eachother selected from O, N and S; R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are thesame or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,(C₁-C₁₆)perfluoroalkyl, (C₃-C₁₀)cycloalkyl, (C₆-C₁₀)aryl(C₁-C₁₆)alkyland substituted or unsubstituted (C₆-C₁₀)aryl; provided when either X orY is O or S, R₁ and R₅, respectively, do not exist; c) one or moreolefinic monomers of the formula (V):

wherein: m is an integer 0, 1 or 2;

is a single bond or a double bond; at least one of R₁₃, R₁₄, R₁₅ and R₁₆is selected from the group consisting of linear or branched(C₆-C₁₆)alkyl, (C₆-C₁₂)aryl(C₁-C₁₆)alkyl, (C₆-C₁₀)aryloxy(C₂-C₁₆)alkyland (C₆-C₁₀)aryl(C₆-C₁₀)aryloxy(C₁-C₁₆)alkyl; the remaining R₁₃, R₁₄,R₁₅ and R₁₆ are the same or different and each independently selectedfrom the group consisting of hydrogen, halogen, a hydrocarbyl orhalohydrocarbyl group selected from methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy,

wherein: Z is selected from the group consisting of: O, CO, C(O)O,OC(O), OC(O)O, S, (CR₁₇R₁₈)_(b), O(CR₁₇R₁₈)_(b), O(CR₁₇R₁₈)_(b)O,C(O)(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)C(O), C(O)O(CR₁₇R₁₈)_(b),(CR₁₇R₁₈)_(b)C(O)O, OC(O)(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)OC(O),(CR₁₇R₁₈)_(b)OC(O)O, (CR₁₇R₁₈)_(b)OC(O)O(CR₁₇R₁₈)_(b),OC(O)O(CR₁₇R₁₈)_(b), S(CR₁₇R₁₈)_(b), (CR₁₇R₁₈)_(b)S, (SiR₁₇R₁₈)_(b),O(SiR₁₇R₁₈)_(b), (SiR₁₇R₁₈)_(b)O, where R₁₇ and R₁₈ are the same ordifferent and each independently selected from hydrogen, methyl, ethyl,linear or branched (C₃-C₁₂)alkyl, substituted or unsubstituted(C₆-C₁₄)aryl, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy,(C₂-C₆)acyl, (C₂-C₆)acyloxy, and substituted or unsubstituted(C₆-C₁₄)aryloxy; and b is an integer from 0 to 12, inclusive; Aryl isselected from the group consisting of substituted or unsubstitutedphenyl, substituted or unsubstituted biphenyl and substituted orunsubstituted naphthyl, substituted or unsubstituted terphenyl,substituted or unsubstituted anthracenyl substituted or unsubstitutedfluorenyl, wherein said substituents are selected from the groupconsisting of halogen, methyl, ethyl, linear or branched (C₃-C₆)alkyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl, methoxy, ethoxy, linear or branched(C₃-C₁₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₀)aryloxy, (C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy andperfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy; k is an integer from 1 to 12; R₂₃,R₂₄ and R₂₅ are the same or different and each independently selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₁₂)alkyl, perfluoro(C₁-C₁₂)alkyl, methoxy, ethoxy, linear orbranched (C₃-C₁₂)alkoxy, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl,perfluoro(C₆-C₁₀)aryl and perfluoro(C₆-C₁₀)aryl(C₁-C₆)alkyl; or R₂₃ andR₂₄ taken together with the intervening carbon atoms to which they areattached to form a substituted or unsubstituted (C₅-C₁₄)cyclic,(C₅-C₁₄)bicyclic or (C₅-C₁₄)tricyclic ring; and Arylene is substitutedor unsubstituted bivalent (C₆-C₁₄)aryl; or one of R₁ and R₂ takentogether with one of R₃ and R₄ and the carbon atoms to which they areattached to form a substituted or unsubstituted (C₅-C₁₄)cyclic,(C₅-C₁₄)bicyclic or (C₅-C₁₄)tricyclic ring; and a) a photosensitizer.17. The kit according to claim 16, which contains at least two distinctfirst and second monomers of formula (V), wherein the first monomer andthe photoacid generator are completely soluble in the second monomer,and when said composition is exposed to suitable actinic radiation for asufficient length of time it forms a substantially transparent filmhaving at least 90 percent of visible light transmission.
 18. The kitaccording to claim 16, which is selected from the group consisting of:5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB), palladiumhexafluoroacetylacetonate (Pd520), 4,4′-di-C₁₀₋₁₃-alkylphenylderivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borates (PAG1) and2-isopropyl-9H-thioxanthen-9-one (ITX); 5-hexylbicyclo[2.2.1]hept-2-ene(HexylNB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtOPhPh), palladium hexafluoroacetylacetonate (Pd520),4,4′-di-C₁₀₋₁₃-alkylphenyl derivatives,tetrakis(2,3,4,5,6-pentafluorophenyl)borates (PAG1) and2-isopropyl-9H-thioxanthen-9-one (ITX); 5-decylbicyclo[2.2.1]hept-2-ene(DecNB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene(NBEtOPhPh), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II)(Pd472), bis(4-n-dodecylphenyl)iodoniumtetrakis(pentafluorophenyl)borate (PAG2) and2-chloro-9H-thioxanthen-9-one (CTX); 5-decylbicyclo[2.2.1]hept-2-ene(DecNB), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II)(Pd472), di(4-n-dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate(PAG2) and 2-chloro-9H-thioxanthen-9-one (CTX); and5-hexylbicyclo[2.2.1]hept-2-ene (HexylNB), palladiumhexafluoroacetylacetonate (Pd520), di(4-n-dodecylphenyl)iodoniumtetrakis(pentafluorophenyl)borate (PAG2) and2-isopropyl-9H-thioxanthen-9-one (ITX).
 19. A film formed from thecomposition of claim
 1. 20. The film formed according to claim 16.